An efficient approach to deoximation using hexachlorodisilane under mild conditions

Abstract

A simple, facile, and efficient procedure for deoximation of oximes to the corresponding ketones and aldehydes with hexachlorodisilane (Si 2 Cl 6 ) in the presence of SiO 2 from good to high yields is described. Apparently, SiO 2 greatly increases the reaction rate and product yield. The proposed procedure is more advantageous than those described previously due to its higher efficiency, milder reaction conditions, shorter reaction, and easier work-up.

AIBN‐Initiated Oxidative Deoximation Reaction: A Metal‐Free and Environmentally‐Friendly Protocol

“…A series of conventional solvents such as EtOAc, EtOH, MeCN, 1,4-dioxane, tetrahydrofuran (THF) and toluene were tested (Table 1, entries 3-8). The reaction in MeCN afforded the highest product yield at 83% (Table 1, entries 5 vs. [2][3][4][6][7][8]. However, considering the environment-protection issues, DMC was the favourable reaction solvent, despite the resulted slight decrease of the product yield in comparison of that of the reaction in MeCN (Table 1, entries 2 vs. 5).…”

“…[3] Moreover, since some oximes can be prepared from non-carbonyl starting materials, deoximation reaction is the key process for the synthesis of the related ketones, and the production of carvone from limonene is a typical example. [4] Deoximation reaction may occur under acidic conditions, but the process usually require stoichiometric/excess additives leading to solid waste generation, [5] or the high-loading and irritant reagents such as Si 2 Cl 6 , [6] SnCl 2 /TiCl 3 [7] and p-toluenesulfonic acid. [8] The oxidative deoximation reaction is another protocol utilizing the oxidation reactionendowed driven force to push forward the conversion.…”

Iron‐Enabled Utilization of Air as the Terminal Oxidant Leading to Aerobic Oxidative Deoximation by Organoselenium Catalysis

“…Synthesis of spice carvone from limonene is one of the typical examples (Scheme ) . However, currently known deoximation methods usually require explosive peroxide oxidants such as H 2 O 2 , or use potentially hazardous cyanide‐containing catalysts or oxidants, or use hazardous reagents such as hexachlorodisilane or halogenated solvents, or use excess hydrochloric acid with iron powder, or use nitrite/nitrate‐containing catalysts or additives ,. Due to the use of the above‐mentioned environmentally‐unfriendly reagents or catalysts, these methods inevitably generate large amounts of wastes.…”